Sulfonated poly(arylene ether) having crosslinkable moiety combined in chain of polymer, sulfonated poly(arylene ether) having crosslinkable moieties combined in polymer and at polymer end group, and polymer electrolyte membrane using sulfonated poly(arylene ether)

Abstract

A sulfonated poly(arylene ether) copolymer that has a crosslinking structure in a chain of a polymer, a sulfonated poly(arylene ether) copolymer that has a crosslinking structure in and at an end of a chain of a polymer, and a polymer electrolyte film that is formed by using them are disclosed. According to the polycondensation reaction of the sulfonated dihydroxy monomer (HO—SAr1-OH), the none sulfonated dihydroxy monomer (HO—Ar—OH), the crosslinkable dihalide monomer (X—CM-X) and the none sulfonated dihalide monomer (X—Ar—X), the poly(arylene ether) copolymer in which the sulfonic acid is included is synthesized. The formed poly(arylene ether) copolymer has the crosslinkable structure in the chain of the polymer. In addition, by carrying out the polycondensation reaction in respects to the crosslinkable monohydroxy monomer or the crosslinkable monohalide monomer, the crosslinking can be formed at the end of the polymer. Through this, the thermal stability, the mechanical stability, the chemical stability, the film formation ability and the like is the same as or better than those of the Nafion film that is currently commercialized and is used as the polymer electrolyte film, and the proton conductivity and the cell performance are excessively improved. In addition, even though it is exposed to the moisture over a long period of time, since there is no change in the property of the electrolyte film, the dimensional stability is high.

What is claimed is: 
     
       1. A poly(arylene ether) copolymer that has a crosslinking structure in a polymer chain that is represented by the following Formula 1 and is sulfonated: 
       
         
           
           
               
               
           
         
         wherein SAr1 is 
       
       
         
           
           
               
               
           
         
         Ar1 represents a first non sulfonated aromatic, Ar2 represents a second non sulfonated aromatic, and CM represents a crosslinkable moiety, wherein SAr1, Ar1, Ar2, and CM are different respectively, 
         wherein k is in the range of 0.001-1.000, s=1-k, b is in the range of 0.001-1.000, d=1-b, n represents a repeating unit of a polymer, and n is an integer and is in the range of 10 to 500, wherein CM is 
       
       
         
           
           
               
               
           
         
       
       in CM, X is a halogen, J is 
       
         
           
           
               
               
           
         
       
       R is a triple bond that is substituted by R1 (ethynyl part) 
       
         
           
           
               
               
           
         
       
       a double bond (vinyl part) 
       
         
           
           
               
               
           
         
       
       in R, G is a single bond in which carbon and carbon are directly connected to each other, —O—, —S— or 
       
         
           
           
               
               
           
         
       
       R1 is H, F, C1˜C5 alkyl or 
       
         
           
           
               
               
           
         
       
       R2 is H, X, or C1˜C5 alkyl, Y is a single bond in which carbon and carbon are directly connected to each other, —O—, —S—, 
       
         
           
           
               
               
           
         
       
       A is a single bond in which carbon and carbon are directly connected to each other, —O—, —S—, 
       
         
           
           
               
               
           
         
       
       E is H, CH 3 , F, CF 3 , C1˜C5 alkyl, or 
       
         
           
           
               
               
           
         
       
       L is H, F, or C1˜C5 alkyl, and 
       
         
           
           
               
               
           
         
       
       is a fluorinated phenylene, and M+ is a counterion having a cation charge. 
     
     
       2. The poly(arylene ether) copolymer that has a crosslinking structure in a polymer chain and is sulfonated according to  claim 1 ,
 Ar1 or Ar2 is 
 
       
         
           
           
               
               
           
         
       
       Y is a single bond in which carbon and carbon are directly connected to each other, —O—, —S—, 
       
         
           
           
               
               
           
         
       
       A is a single bond in which carbon and carbon are directly connected to each other, —O—, —S—, 
       
         
           
           
               
               
           
         
       
       E is H, CH3, F, CF3, C1˜C5 alkyl or 
       
         
           
           
               
               
           
         
         L is H, F, or C1˜C5 alkyl, 
       
       
         
           
           
               
               
           
         
       
       is a fluorinated phenylene. 
     
     
       3. The poly(arylene ether) copolymer that has a crosslinking structure in a polymer chain and is sulfonated according to  claim 2 , wherein the counterion that has the cation charge is potassium ion, sodium ion or alkyl amine. 
     
     
       4. The poly(arylene ether) copolymer that has a crosslinking structure in a polymer chain and is sulfonated according to  claim 1 , wherein the sulfonated poly(arylene ether) copolymer of Formula 1 is formed according to the following Reaction Equation 1 which includes the polycondensation reaction of a sulfonated dihydroxy monomer (HO—SAr1-OH), a non sulfonated dihydroxy monomer (HO—Ar2-OH), a crosslinkable dihalide monomer (X-CM-X), and a non sulfonated dihalide monomer (X—Ar1-X): 
       
         
           
           
               
               
           
         
       
     
     
       5. The poly(arylene ether) copolymer that has a crosslinking structure in a polymer chain and is sulfonated according to  claim 4 , wherein the polycondensation reaction is carried out in the presence of a solvent that includes a base, an azeotropic solvent, and a polar solvent at a temperature in the range of 0˜300° C. for 1 to 100 hours. 
     
     
       6. The poly(arylene ether) copolymer that has a crosslinking structure in a polymer chain and is sulfonated according to  claim 5 , wherein the base is an inorganic base that is selected from an alkali metal, hydroxides of an alkali earth metal, carbonate and sulfate, or an organic base that is selected from ammonia and general amines, the polar solvent is a non protonic polar solvent or a protonic polar solvent, N-methylpyrrolidone (NMP), dimethyl formamide (DMF), N,N-dimethyl acetamide (DMAc) or dimethyl sulfoxide (DMSO) is used as the non protonic polar solvent, methylene chloride (CH2Cl2), chloroform (CH3Cl) or tetrahydrofurane (THF) is used as the protonic polar solvent, and the azeotropic solvent is benzene, toluene or xylene.